CN103890860B - Graphene-based laminates including the polymeric layer of doping - Google Patents
Graphene-based laminates including the polymeric layer of doping Download PDFInfo
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- CN103890860B CN103890860B CN201280042456.3A CN201280042456A CN103890860B CN 103890860 B CN103890860 B CN 103890860B CN 201280042456 A CN201280042456 A CN 201280042456A CN 103890860 B CN103890860 B CN 103890860B
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 114
- 229910021389 graphene Inorganic materials 0.000 title claims abstract description 109
- 239000013047 polymeric layer Substances 0.000 title abstract description 38
- 239000000758 substrate Substances 0.000 claims abstract description 55
- 239000000126 substance Substances 0.000 claims description 43
- 239000002608 ionic liquid Substances 0.000 claims description 33
- 229920000642 polymer Polymers 0.000 claims description 31
- -1 1-octyl Chemical group 0.000 claims description 20
- 150000001450 anions Chemical class 0.000 claims description 16
- 239000000203 mixture Substances 0.000 claims description 16
- 125000002769 thiazolinyl group Chemical group 0.000 claims description 15
- 230000003252 repetitive effect Effects 0.000 claims description 12
- 150000001875 compounds Chemical class 0.000 claims description 10
- 125000000217 alkyl group Chemical group 0.000 claims description 9
- 125000003118 aryl group Chemical group 0.000 claims description 9
- 229920001577 copolymer Polymers 0.000 claims description 9
- 238000004519 manufacturing process Methods 0.000 claims description 9
- 239000001257 hydrogen Substances 0.000 claims description 8
- 229910052739 hydrogen Inorganic materials 0.000 claims description 8
- 125000003368 amide group Chemical group 0.000 claims description 7
- 125000005587 carbonate group Chemical group 0.000 claims description 7
- 150000001768 cations Chemical class 0.000 claims description 7
- 239000001913 cellulose Substances 0.000 claims description 7
- 229920002678 cellulose Polymers 0.000 claims description 7
- 125000004185 ester group Chemical group 0.000 claims description 7
- 150000003949 imides Chemical class 0.000 claims description 7
- 125000000304 alkynyl group Chemical group 0.000 claims description 6
- 125000000753 cycloalkyl group Chemical group 0.000 claims description 6
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 5
- 150000002170 ethers Chemical class 0.000 claims description 5
- 239000004926 polymethyl methacrylate Substances 0.000 claims description 5
- 125000000472 sulfonyl group Chemical group *S(*)(=O)=O 0.000 claims description 5
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 4
- 150000001449 anionic compounds Chemical class 0.000 claims description 4
- 229910001412 inorganic anion Inorganic materials 0.000 claims description 4
- 150000002891 organic anions Chemical group 0.000 claims description 4
- 229920003229 poly(methyl methacrylate) Polymers 0.000 claims description 4
- XLJSMWDFUFADIA-UHFFFAOYSA-N 1,3-diethylimidazol-1-ium Chemical compound CCN1C=C[N+](CC)=C1 XLJSMWDFUFADIA-UHFFFAOYSA-N 0.000 claims description 3
- KAIPKTYOBMEXRR-UHFFFAOYSA-N 1-butyl-3-methyl-2h-imidazole Chemical compound CCCCN1CN(C)C=C1 KAIPKTYOBMEXRR-UHFFFAOYSA-N 0.000 claims description 3
- QQAJQOSQIHCXPL-UHFFFAOYSA-N 1-butyl-3-methyl-2h-pyridine Chemical compound CCCCN1CC(C)=CC=C1 QQAJQOSQIHCXPL-UHFFFAOYSA-N 0.000 claims description 3
- REACWASHYHDPSQ-UHFFFAOYSA-N 1-butylpyridin-1-ium Chemical compound CCCC[N+]1=CC=CC=C1 REACWASHYHDPSQ-UHFFFAOYSA-N 0.000 claims description 3
- DVNFMHWKXQEEAH-UHFFFAOYSA-N 1-dodecyl-3-methyl-2h-imidazole Chemical compound CCCCCCCCCCCCN1CN(C)C=C1 DVNFMHWKXQEEAH-UHFFFAOYSA-N 0.000 claims description 3
- UCRIXEWTILHNCG-UHFFFAOYSA-N 1-ethyl-2h-pyridine Chemical compound CCN1CC=CC=C1 UCRIXEWTILHNCG-UHFFFAOYSA-N 0.000 claims description 3
- IBZJNLWLRUHZIX-UHFFFAOYSA-N 1-ethyl-3-methyl-2h-imidazole Chemical compound CCN1CN(C)C=C1 IBZJNLWLRUHZIX-UHFFFAOYSA-N 0.000 claims description 3
- WGVGZVWOOMIJRK-UHFFFAOYSA-N 1-hexyl-3-methyl-2h-imidazole Chemical compound CCCCCCN1CN(C)C=C1 WGVGZVWOOMIJRK-UHFFFAOYSA-N 0.000 claims description 3
- FIOYZGZRZWNKTB-UHFFFAOYSA-N 1-methyl-3-tetradecyl-2h-imidazole Chemical compound CCCCCCCCCCCCCCN1CN(C)C=C1 FIOYZGZRZWNKTB-UHFFFAOYSA-N 0.000 claims description 3
- 229910017048 AsF6 Inorganic materials 0.000 claims description 3
- ITIABACYRWQDBU-UHFFFAOYSA-N C(C)N1CC(=CC=C1)C Chemical compound C(C)N1CC(=CC=C1)C ITIABACYRWQDBU-UHFFFAOYSA-N 0.000 claims description 3
- 229910016861 F9SO3 Inorganic materials 0.000 claims description 3
- 239000002033 PVDF binder Substances 0.000 claims description 3
- 229920003171 Poly (ethylene oxide) Polymers 0.000 claims description 3
- 229910001914 chlorine tetroxide Inorganic materials 0.000 claims description 3
- JZMJDSHXVKJFKW-UHFFFAOYSA-M methyl sulfate(1-) Chemical compound COS([O-])(=O)=O JZMJDSHXVKJFKW-UHFFFAOYSA-M 0.000 claims description 3
- VLTRZXGMWDSKGL-UHFFFAOYSA-M perchlorate Chemical compound [O-]Cl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-M 0.000 claims description 3
- 229920002981 polyvinylidene fluoride Polymers 0.000 claims description 3
- 229920001451 polypropylene glycol Polymers 0.000 claims description 2
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims 2
- SWWCIHVYFYTXDK-UHFFFAOYSA-N 1,3-dimethyl-2h-imidazole Chemical compound CN1CN(C)C=C1 SWWCIHVYFYTXDK-UHFFFAOYSA-N 0.000 claims 1
- VBZTZOBDNBFJDW-UHFFFAOYSA-N 1-butyl-3,4-dimethyl-2H-pyridine Chemical class C(CCC)N1CC(=C(C=C1)C)C VBZTZOBDNBFJDW-UHFFFAOYSA-N 0.000 claims 1
- NUUDMTGMAZJCBY-UHFFFAOYSA-N 1-decyl-3-methyl-2h-imidazole Chemical compound CCCCCCCCCCN1CN(C)C=C1 NUUDMTGMAZJCBY-UHFFFAOYSA-N 0.000 claims 1
- LTKMTXLIAZLQHS-UHFFFAOYSA-N 1-methylpyridine Chemical compound CN1C=CC=C=C1 LTKMTXLIAZLQHS-UHFFFAOYSA-N 0.000 claims 1
- 239000004698 Polyethylene Substances 0.000 claims 1
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Natural products C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims 1
- 239000000835 fiber Substances 0.000 claims 1
- 229920000573 polyethylene Polymers 0.000 claims 1
- 125000003011 styrenyl group Chemical class [H]\C(*)=C(/[H])C1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 claims 1
- 239000010410 layer Substances 0.000 abstract description 69
- 150000003839 salts Chemical class 0.000 description 16
- 238000000034 method Methods 0.000 description 11
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 description 10
- 229910052799 carbon Inorganic materials 0.000 description 7
- 125000005843 halogen group Chemical group 0.000 description 7
- 239000000463 material Substances 0.000 description 7
- 238000005530 etching Methods 0.000 description 6
- 150000002431 hydrogen Chemical class 0.000 description 6
- JNCMHMUGTWEVOZ-UHFFFAOYSA-N F[CH]F Chemical compound F[CH]F JNCMHMUGTWEVOZ-UHFFFAOYSA-N 0.000 description 5
- 229910019142 PO4 Inorganic materials 0.000 description 5
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 5
- 239000003054 catalyst Substances 0.000 description 5
- 238000005229 chemical vapour deposition Methods 0.000 description 5
- 125000004093 cyano group Chemical group *C#N 0.000 description 5
- VUWZPRWSIVNGKG-UHFFFAOYSA-N fluoromethane Chemical compound F[CH2] VUWZPRWSIVNGKG-UHFFFAOYSA-N 0.000 description 5
- 150000007857 hydrazones Chemical class 0.000 description 5
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 5
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 description 5
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 5
- 239000010452 phosphate Substances 0.000 description 5
- 150000003254 radicals Chemical class 0.000 description 5
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 4
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 4
- 150000001336 alkenes Chemical class 0.000 description 4
- 229920001519 homopolymer Polymers 0.000 description 4
- 125000005504 styryl group Chemical group 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 150000001721 carbon Chemical group 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- 239000010949 copper Substances 0.000 description 3
- 229910052736 halogen Inorganic materials 0.000 description 3
- 150000002367 halogens Chemical class 0.000 description 3
- 229910052738 indium Inorganic materials 0.000 description 3
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- OFBQJSOFQDEBGM-UHFFFAOYSA-N n-pentane Natural products CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 3
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 3
- JWGNRZBHPGAAOQ-UHFFFAOYSA-N 1-hexyl-3-methyl-2H-pyridine Chemical compound C(CCCCC)N1CC(=CC=C1)C JWGNRZBHPGAAOQ-UHFFFAOYSA-N 0.000 description 2
- MCTWTZJPVLRJOU-UHFFFAOYSA-N 1-methyl-1H-imidazole Chemical compound CN1C=CN=C1 MCTWTZJPVLRJOU-UHFFFAOYSA-N 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- 239000004642 Polyimide Substances 0.000 description 2
- 239000004372 Polyvinyl alcohol Substances 0.000 description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 2
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 2
- 150000001335 aliphatic alkanes Chemical class 0.000 description 2
- 229910045601 alloy Inorganic materials 0.000 description 2
- 239000000956 alloy Substances 0.000 description 2
- 239000011651 chromium Substances 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- ZSWFCLXCOIISFI-UHFFFAOYSA-N cyclopentadiene Chemical compound C1C=CC=C1 ZSWFCLXCOIISFI-UHFFFAOYSA-N 0.000 description 2
- 125000002704 decyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- 238000000151 deposition Methods 0.000 description 2
- 230000008021 deposition Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000007792 gaseous phase Substances 0.000 description 2
- 239000010931 gold Substances 0.000 description 2
- PJXISJQVUVHSOJ-UHFFFAOYSA-N indium(iii) oxide Chemical compound [O-2].[O-2].[O-2].[In+3].[In+3] PJXISJQVUVHSOJ-UHFFFAOYSA-N 0.000 description 2
- 239000007791 liquid phase Substances 0.000 description 2
- 239000011777 magnesium Substances 0.000 description 2
- 239000011572 manganese Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 229920000139 polyethylene terephthalate Polymers 0.000 description 2
- 239000005020 polyethylene terephthalate Substances 0.000 description 2
- 229920001721 polyimide Polymers 0.000 description 2
- 229920002451 polyvinyl alcohol Polymers 0.000 description 2
- 239000001294 propane Substances 0.000 description 2
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 2
- 239000010948 rhodium Substances 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- 239000010703 silicon Substances 0.000 description 2
- 238000004528 spin coating Methods 0.000 description 2
- 239000004575 stone Substances 0.000 description 2
- 150000003457 sulfones Chemical class 0.000 description 2
- 239000010936 titanium Substances 0.000 description 2
- BKOOMYPCSUNDGP-UHFFFAOYSA-N 2-methylbut-2-ene Chemical group CC=C(C)C BKOOMYPCSUNDGP-UHFFFAOYSA-N 0.000 description 1
- 229910000906 Bronze Inorganic materials 0.000 description 1
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- 229910000570 Cupronickel Inorganic materials 0.000 description 1
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 1
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 229910052770 Uranium Inorganic materials 0.000 description 1
- 150000001252 acrylic acid derivatives Chemical class 0.000 description 1
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 238000001505 atmospheric-pressure chemical vapour deposition Methods 0.000 description 1
- 239000010974 bronze Substances 0.000 description 1
- 239000001273 butane Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002091 carbon monoxide Inorganic materials 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- YOCUPQPZWBBYIX-UHFFFAOYSA-N copper nickel Chemical compound [Ni].[Cu] YOCUPQPZWBBYIX-UHFFFAOYSA-N 0.000 description 1
- KUNSUQLRTQLHQQ-UHFFFAOYSA-N copper tin Chemical compound [Cu].[Sn] KUNSUQLRTQLHQQ-UHFFFAOYSA-N 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000003618 dip coating Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000005684 electric field Effects 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 description 1
- 229910052732 germanium Inorganic materials 0.000 description 1
- GNPVGFCGXDBREM-UHFFFAOYSA-N germanium atom Chemical compound [Ge] GNPVGFCGXDBREM-UHFFFAOYSA-N 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 125000004836 hexamethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[*:1] 0.000 description 1
- 150000002460 imidazoles Chemical class 0.000 description 1
- 238000009616 inductively coupled plasma Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000004518 low pressure chemical vapour deposition Methods 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 239000011733 molybdenum Substances 0.000 description 1
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 150000004767 nitrides Chemical class 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 238000000623 plasma-assisted chemical vapour deposition Methods 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 150000003222 pyridines Chemical class 0.000 description 1
- NIFIFKQPDTWWGU-UHFFFAOYSA-N pyrite Chemical compound [Fe+2].[S-][S-] NIFIFKQPDTWWGU-UHFFFAOYSA-N 0.000 description 1
- 229910052683 pyrite Inorganic materials 0.000 description 1
- 239000011028 pyrite Substances 0.000 description 1
- 238000001289 rapid thermal chemical vapour deposition Methods 0.000 description 1
- 239000012495 reaction gas Substances 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 1
- VSZWPYCFIRKVQL-UHFFFAOYSA-N selanylidenegallium;selenium Chemical compound [Se].[Se]=[Ga].[Se]=[Ga] VSZWPYCFIRKVQL-UHFFFAOYSA-N 0.000 description 1
- 239000002356 single layer Substances 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 229910052715 tantalum Inorganic materials 0.000 description 1
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 description 1
- 238000002230 thermal chemical vapour deposition Methods 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 239000010937 tungsten Substances 0.000 description 1
- JFALSRSLKYAFGM-UHFFFAOYSA-N uranium(0) Chemical compound [U] JFALSRSLKYAFGM-UHFFFAOYSA-N 0.000 description 1
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B5/00—Non-insulated conductors or conductive bodies characterised by their form
- H01B5/14—Non-insulated conductors or conductive bodies characterised by their form comprising conductive layers or films on insulating-supports
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
- H01B1/04—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of carbon-silicon compounds, carbon or silicon
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B3/00—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties
- H01B3/18—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances
- H01B3/30—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances plastics; resins; waxes
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/30—Self-sustaining carbon mass or layer with impregnant or other layer
Abstract
Disclose the graphene-based laminates of a kind of polymeric layer including doping.Described graphene-based laminates comprises the steps that substrate；Graphene layer, is arranged in substrate and includes at least one of which；The polymeric layer of doping, is arranged at least one surface of graphene layer and includes organic adulterant.
Description
Technical field
It relates to a kind of graphene-based laminates, more particularly, it relates to a kind of polymeric layer including doping
Graphene-based laminates, the polymeric layer of this doping can control the electric conductivity of graphene layer and protect the stone of graphene-based laminates
Ink alkene layer.
Background technology
Graphene is a kind of material with high conductivity and stable electrology characteristic, mechanical property and chemical characteristic.
The electron mobility of Graphene is about 100 times of silicon high, and current flow rate is about 100 times high of copper.Therefore, recent pin
The various aspects of Graphene are the most much studied.
Graphene is only made up of the carbon with relatively small atomic wts, is thus susceptible to be processed into one-dimensional or two-dimensional nano figure
Case.According to the various chemical bonds of carbon, Graphene can be applicable to control semiconducting character or the conductive characteristic of material, and can apply
In manufacturing the most such as sensor and the functional devices of storage device.
Transparency electrode field is the application that a market of Graphene quickly increases.Owing to using Indium sesquioxide. for a long time
Stannum (ITO) is as main transparent electrode material so that the problem that such as indium resource exhaustion and cost increase has occurred.And
And, indium is breakable, is not therefore suitable for collapsible or ductile flexible product.Due to these reasons, for exploitation stone
Ink alkene is as the substitute of indium, existing increasing demand.
But, also it is not carried out being effectively synthesized and shift or suitable adulterant of Graphene, the most currently available
Graphene-based electrode assembly is it cannot be guaranteed that scale required for gratifying quality and actual production.
Summary of the invention
Technical problem
The present invention provides the graphene-based laminates of a kind of polymeric layer including doping, and the polymeric layer of this doping is controlled
The electric conductivity of graphene layer processed and protect the graphene layer of graphene-based laminates.
Technical scheme
According to an aspect of the present invention, graphene-based laminates includes: substrate；Graphene layer, is arranged in substrate
And including at least one of which；The polymeric layer of doping, is arranged at least one surface of graphene layer and includes organic
Adulterant.
Described substrate can have the transparency, flexibility, the characteristic of ductility or the combination of these characteristics.
Described substrate may utilize to be had the polymer of repetitive and manufactures, and this repetitive includes from by replacing or not taking
The thiazolinyl in generation, substituted or unsubstituted ester group, substituted or unsubstituted ether, substituted or unsubstituted acrylate-based, replacement
Or it is unsubstituted carbonate group, substituted or unsubstituted styryl, substituted or unsubstituted amide groups, substituted or unsubstituted
At least one selected in the group of imide and substituted or unsubstituted sulfuryl composition.Described substrate may utilize cellulose or bag
Include the polymer of cellulose and manufacture.The quantity of repetitive can be in the range of about 1 to about 500, in certain embodiments
Can be in the range of about 1 to about 300.Polymer can be homopolymer or copolymer.Such as, polymer can be homopolymer.
In copolymer, the ratio of different repeat units can be controlled as scope commonly used in the art aptly, such as, control be
The scope of 0.01:0.99 to 0.99:0.01.
As used herein, " thiazolinyl " can be " substituted or unsubstituted C2～C20 thiazolinyl ", for example, it may be " take
Generation or unsubstituted C2～C10 thiazolinyl ".Term " replaces " can refer to that replacement has following radicals: halogen atom, replacement have halogen former
C1～C20 alkyl (such as, the CF of son3、CHF2、CH2F、CCl3Deng), hydroxyl, nitro, cyano group, amino, amidino groups, hydrazine, hydrazone, carboxyl
Or its salt, sulfonic group or its salt, phosphate or its salt, C1～C20 alkyl, C2～C20 thiazolinyl, C2～C20 alkynyl, C1～C20
Miscellaneous alkyl, C6～C20 aryl, C6～C20 aralkyl, C6～C20 heteroaryl or C6～C20 heteroarylalkyl.
As used herein, " ester group " refers to the group represented with-COOR, and " carbonate group " refers to-OC (=O)
(OR) group represented, " amide groups " refers to-RC (=O) NR1The group represented, " imide " refers to-R1C(=O)N(R)
C(=O)R2The group represented, " sulfone " refers to-RSO2R1The group represented.In these chemical formulas, R, R1And R2All can be independent
Ground is hydrogen, C1～C10 alkyl or C6～C20 aryl.
As used herein, " including the polymer of cellulose " refers to the polymer of cellulose, and is to have
The polymer of repetitive, this repetitive includes from by substituted or unsubstituted thiazolinyl, substituted or unsubstituted ester group, replacement
Or it is unsubstituted ether, substituted or unsubstituted carbonate group acrylate-based, substituted or unsubstituted, substituted or unsubstituted
Styryl, substituted or unsubstituted amide groups, substituted or unsubstituted imide and substituted or unsubstituted sulfuryl composition
Group in select at least one.
In certain embodiments, organic blended dose of the polymeric layer of doping can be ionic liquid, and ionic liquid can wrap
Include the compound represented by formula 1 below and/or chemical formula 2:
[chemical formula 1]
In chemical formula 1, R1And R2Can be mutually the same or different from each other, and all can independently be hydrogen, replacement or
Unsubstituted C1～C16 alkyl, substituted or unsubstituted C2～C16 thiazolinyl, substituted or unsubstituted C2～C16 alkynyl, replacement
Or unsubstituted C3～C16 cycloalkyl, substituted or unsubstituted C6～C16 aryl or substituted or unsubstituted C6～C20 are miscellaneous
Aryl；X-The anion of ionic liquid can be represented.
[chemical formula 2]
In chemical formula 2, R3And R4Can be mutually the same or different from each other, and all can independently be hydrogen, replacement or
Unsubstituted C1～C16 alkyl, substituted or unsubstituted C2～C16 thiazolinyl, substituted or unsubstituted C2～C16 alkynyl, replacement
Or unsubstituted C3～C16 cycloalkyl, substituted or unsubstituted C6～C16 aryl or substituted or unsubstituted C6～C20 are miscellaneous
Aryl；X-The anion of ionic liquid can be represented.
For chemical formula 1 and/or chemical formula 2, term " replaces " and refers to that replacement has a following radicals: halogen atom, replaces and has halogen
C1～C20 alkyl (such as, the CF of element atom3、CHF2、CH2F、CCl3Deng), hydroxyl, nitro, cyano group, amino, amidino groups, hydrazine, hydrazone,
Carboxyl or its salt, sulfonic group or its salt, phosphate or its salt, C1～C20 alkyl, C2～C20 thiazolinyl, C2～C20 alkynyl, C1～
The miscellaneous alkyl of C20, C6～C20 aryl, C6～C20 aralkyl, C6～C20 heteroaryl or C6～C20 heteroarylalkyl.
Cation in chemical formula 1 can include from by 1,3-methylimidazole, 1,3-diethyl imidazolium, 1-ethyl-
3-Methylimidazole., 1-butyl-3-Methylimidazole., 1-hexyl-3-Methylimidazole., 1-octyl group-3-Methylimidazole., 1-last of the ten Heavenly stems
The group of base-3-Methylimidazole., 1-dodecyl-3-Methylimidazole. and 1-myristyl-3-Methylimidazole. composition is selected
At least one selected.
Cation in chemical formula 2 can include from by 1-picoline, 1-ethylpyridine, 1-butyl-pyridinium, 1-
Ethyl-3-picoline, 1-butyl-3-picoline, 1-hexyl-3-picoline and 1-butyl-3,4-dimethyl
At least one selected in the group of pyridine composition.
The anion of the ionic liquid of chemical formula 1 or 2 can be organic anion or inorganic anion.Such as, chemical formula 1
Or the anion of the ionic liquid of 2 can include from by Br-、Cl-、I-、BF4 -、PF6 -、ClO4 -、NO3 -、AlCl4 -、Al2Cl7 -、
AsF6 -、SbF6 -、CH3COO-、CF3COO-、CH3SO3 -、C2H5SO3 -、CH3SO4 -、C2H5SO4 -、CF3SO3 -、(CF3SO2)2N-、
(CF3SO2)3C-、(CF3CF2SO2)2N-、C4F9SO3 -、C3F7COO-(CF3SO2)(CF3CO)N-The group of composition selects at least
A kind of.In certain embodiments, the polymeric layer of doping may also include can be compatible with described ionic liquid polymer.Such as,
Can include from by polyvinyl alcohol, polymethyl methacrylate, poly(ethylene oxide), poly-by the polymer compatible with described ionic liquid
At least one selected in the group of expoxy propane, polyvinylidene fluoride and their copolymer composition.Different repetitions in copolymer
The ratio of unit can be scope commonly used in the art by controlling aptly, such as, controls as 0.01:0.99 to 0.99:
The scope of 0.01.
Invention effect
As it has been described above, according to one or more embodiment of the present invention, graphene-based laminates may be included in Graphene
The polymeric layer of the doping at least one surface of layer, to control the electric conductivity of graphene layer.The polymeric layer of doping can be protected
Protect graphene layer and stablize graphene layer further.
Accompanying drawing explanation
Fig. 1 is the perspective schematic view according to the graphene-based laminates that embodiment of the disclosure；
Fig. 2 is the sectional view of the graphene-based laminates according to the Fig. 1 that embodiment of the disclosure；
Fig. 3 is the sectional view of the graphene-based laminates of Fig. 1 of another embodiment according to the disclosure.
For preferred embodiment of the present invention
Hereinafter, with reference to the accompanying drawings embodiments of the invention are described below in greater detail.
Fig. 1 is the perspective schematic view according to the graphene-based laminates 100 that embodiment of the disclosure.Fig. 2 and Fig. 3 is root
Sectional view according to the graphene-based laminates of the Fig. 1 that embodiment of the disclosure.
With reference to Fig. 1, graphene-based laminates (laminates based on Graphene) 100 can include substrate 110, be arranged on substrate
Graphene layer 120 on 110 and the polymeric layer 130 of doping being arranged at least one surface of graphene layer 120.
Graphene-based laminates 100 can be used for manufacturing the electric field crystal such as of future generation needing flexible and/or extension characteristics
The electrode (particularly transparency electrode) of the various electric device of pipe or diode etc., or be used for manufacturing Graphene transparent electrical
Pole, this graphene transparent electrode becomes the electronic technology of problem for area of solar cell, touch sensor field and flexibility
Photovoltaic applications in field.
Substrate 110 can have the transparency, flexibility, the characteristic of ductility or the combination of these characteristics.Substrate 110 can include tool
Have the polymer of repetitive, this repetitive include from by substituted or unsubstituted thiazolinyl, substituted or unsubstituted ester group, take
Generation or unsubstituted ether, substituted or unsubstituted carbonate group acrylate-based, substituted or unsubstituted, replacement or unsubstituted
Styryl, substituted or unsubstituted amide groups, substituted or unsubstituted imide and replacement and unsubstituted sulfuryl group
At least one selected in the group become.The quantity of repetitive can be in the range of about 1 to about 500, in certain embodiments
Can be in the range of about 1 to about 300.Polymer can be homopolymer or copolymer.Such as, polymer can be homopolymer.
In copolymer, the ratio of different repeat units can be controlled aptly as the usual range in this area.
As used herein, " thiazolinyl " can be " substituted or unsubstituted C2～C20 thiazolinyl ", for example, it may be " take
Generation or unsubstituted C2～C10 thiazolinyl ".Term " replaces " can refer to that replacement has following radicals: halogen atom, replacement have halogen former
C1～C20 alkyl (such as, the CF of son3、CHF2、CH2F、CCl3Deng), hydroxyl, nitro, cyano group, amino, amidino groups, hydrazine, hydrazone, carboxyl
Or its salt, sulfonic group or its salt, phosphate or its salt, C1～C20 alkyl, C2～C20 thiazolinyl, C2～C20 alkynyl, C1～C20
Miscellaneous alkyl, C6～C20 aryl, C6～C20 aralkyl, C6～C20 heteroaryl or C6～C20 heteroarylalkyl.
As used herein, " ester group " refers to the group represented with-COOR, and " carbonate group " refers to-OC (=O)
(OR) group represented, " amide groups " refers to-RC (=O) NR1The group represented, " imide " refers to-R1C(=O)N(R)
C(=O)R2The group represented, " sulfone " refers to-RSO2R1The group represented.In these chemical formulas, R, R1And R2All can be independent
Ground is hydrogen, C1～C10 alkyl or C6～C20 aryl.
As used herein, " including the polymer of cellulose " refers to the polymer of cellulose, and is to have
The polymer of repetitive, this repetitive includes from by substituted or unsubstituted thiazolinyl, substituted or unsubstituted ester group, replacement
Or it is unsubstituted ether, substituted or unsubstituted carbonate group acrylate-based, substituted or unsubstituted, substituted or unsubstituted
Styryl, substituted or unsubstituted amide groups, substituted or unsubstituted imide and substituted or unsubstituted sulfuryl composition
Group in select at least one.
Polymer for substrate can be such as polymethyl methacrylate (PMMA), polyethylene terephthalate
(PET), PEN (PEN), Merlon (PC) or polyimides (PI).
Graphene layer 120 may be formed in substrate 110.The side forming graphene layer 120 will be described subsequently in substrate 110
Method.
Graphene layer 120 can be graphene layer or graphene film, and plurality of carbon atom is the most covalently bound to be formed
Multi-ring aromatic molecules.
The most covalently bound carbon atom can be formed but be not limited to hexatomic ring as shown in Figure 1, as basic repetition
Unit.Covalently bound carbon atom can also form five-membered ring, heptatomic ring etc..
Graphene layer 120 can be but not limited to monolayer.Graphene layer 120 can also be multilamellar.Such as, graphene layer
120 can be 2 layers to 50 layers.
Graphene layer 120 can have large area, such as, has the about 1mm length to about 1000m in the lateral or vertical direction.
The polymeric layer 130 of doping may be disposed at least one surface of graphene layer 120 and includes organic mixing
Miscellaneous dose.The polymeric layer 130 of doping can control the electric conductivity of graphene layer 120 and can protect graphene layer 120.
As it is shown in figure 1, the polymeric layer 130 of doping may be disposed between substrate 110 and graphene layer 120.But, this
Inventive embodiment is not limited to this.Such as, as in figure 2 it is shown, the polymeric layer 130 of doping may be disposed on graphene layer 120.
Such as, as it is shown on figure 3, the polymeric layer 130 of doping can include that be arranged between substrate 110 and graphene layer 120 first mixes
Miscellaneous polymeric layer 130a and the second polymeric layer 130b adulterated being arranged on graphene layer 120.Form the polymerization of doping
The method of nitride layer 130 will describe subsequently.
Organic blended dose in the polymeric layer 130 of doping can be ionic liquid.The polymeric layer 130 of doping is all right
Including polymer.
Ionic liquid in the polymeric layer 130 of doping refers to be made up of ionic bond but at room temperature with the thing of liquid phase existence
Matter.That is, ionic liquid be made up of ionic bond and have based on cation and the combination of anion various physical characteristic and
The salt of the liquid phase of chemical characteristic.
Ionic liquid can be chemically stable and heat-staple, and can have highly polar and high ion-conductivity.From
Sub-liquid can be as adulterant, it is possible to control the electronic state of Graphene by interacting with Graphene.
In certain embodiments, in graphene-based laminates 100, the ionic liquid in the polymeric layer 130 of doping can
Including the compound represented by formula 1 below.
[chemical formula 1]
The ionic liquid of chemical formula 1 can be imidazole salt ionic liquid.In chemical formula 1, R1And R2Can be each other
Identical or different from each other, and all can independently be hydrogen, substituted or unsubstituted C1～C16 alkyl, substituted or unsubstituted
C2～C16 thiazolinyl, substituted or unsubstituted C2～C16 alkynyl, substituted or unsubstituted C3～C16 cycloalkyl, replacement or do not take
C6～the C16 aryl in generation or substituted or unsubstituted C6～C20 heteroaryl；X-can represent the anion of ionic liquid.
About chemical formula 1, term " replaces " and refers to that replacement has a following radicals: halogen atom, replace the C1 having halogen atom
～C20 alkyl (such as, CF3、CHF2、CH2F、CCl3Deng), hydroxyl, nitro, cyano group, amino, amidino groups, hydrazine, hydrazone, carboxyl or its
Salt, sulfonic group or its salt, phosphate or its salt, C1～C20 alkyl, C2～C20 thiazolinyl, C2～C20 alkynyl, the miscellaneous alkane of C1～C20
Base, C6～C20 aryl, C6～C20 aralkyl, C6～C20 heteroaryl or C6～C20 heteroarylalkyl.
Cation in chemical formula 1 can include from by 1,3-methylimidazole, 1,3-diethyl imidazolium, 1-ethyl-
3-Methylimidazole., 1-butyl-3-Methylimidazole., 1-hexyl-3-Methylimidazole., 1-octyl group-3-Methylimidazole., 1-last of the ten Heavenly stems
The group of base-3-Methylimidazole., 1-dodecyl-3-Methylimidazole. and 1-myristyl-3-Methylimidazole. composition is selected
At least one selected.
Anion in chemical formula 1 can be organic anion or inorganic anion.Such as, the anion in chemical formula 1
Can include from by Br-、Cl-、I-、BF4 -、PF6 -、ClO4 -、NO3 -、AlCl4 -、Al2Cl7 -、AsF6 -、SbF6 -、CH3COO-、CF3COO-、
CH3SO3 -、C2H5SO3 -、CH3SO4 -、C2H5SO4 -、CF3SO3 -、(CF3SO2)2N-、(CF3SO2)3C-、(CF3CF2SO2)2N-、
C4F9SO3 -、C3F7COO-(CF3SO2)(CF3CO)N-At least one selected in the group of composition.
In certain embodiments, in graphene-based laminates 100, the ionic liquid in the polymeric layer 130 of doping can
Including the compound represented by formula 2 below.In other embodiments, in graphene-based laminates 100, gathering of doping
Ionic liquid in compound layer 130 can include the compound represented by chemical formula 1 and 2, or optionally can include by changing
The compound that formula 2 represents.
[chemical formula 2]
The ionic liquid of chemical formula 2 can be pyridine salt ionic liquid.In chemical formula 2, R3And R4Can be each other
Identical or different from each other, and all can independently be hydrogen, substituted or unsubstituted C1～C16 alkyl, substituted or unsubstituted
C2～C16 thiazolinyl, substituted or unsubstituted C2～C16 alkynyl, substituted or unsubstituted C3～C16 cycloalkyl, replacement or do not take
C6～the C16 aryl in generation or substituted or unsubstituted C6～C20 heteroaryl；X-The anion of ionic liquid can be represented.
About chemical formula 2, term " replaces " and refers to that replacement has a following radicals: halogen atom, replace the C1 having halogen atom
～C20 alkyl (such as, CF3、CHF2、CH2F、CCl3Deng), hydroxyl, nitro, cyano group, amino, amidino groups, hydrazine, hydrazone, carboxyl or its
Salt, sulfonic group or its salt, phosphate or its salt, C1～C20 alkyl, C2～C20 thiazolinyl, C2～C20 alkynyl, the miscellaneous alkane of C1～C20
Base, C6～C20 aryl, C6～C20 aralkyl, C6～C20 heteroaryl or C6～C20 heteroarylalkyl.
Cation in chemical formula 2 can include from by 1-picoline, 1-ethylpyridine, 1-butyl-pyridinium, 1-
Ethyl-3-picoline, 1-butyl-3-picoline, 1-hexyl-3-picoline and 1-butyl-3,4-dimethyl
At least one selected in the group of pyridine composition.
The anion of chemical formula 2 can be organic anion or inorganic anion.Anion in chemical formula 2 can include with
Above in conjunction with at least one in the anion that the anion described by chemical formula 1 is identical, and thereof will be omitted it and retouch in detail
State.
In certain embodiments, may further include can be with for the polymeric layer 130 of the doping of graphene-based laminates 100
The polymer that described ionic liquid is compatible.
There is no particular restriction for polymer that can be compatible with described ionic liquid, can be compatible with described ionic liquid
Any polymer.Such as, can include from by polyvinyl alcohol, poly-methyl methacrylate by the polymer compatible with described ionic liquid
At least one selected in the group of ester, poly(ethylene oxide), poly(propylene oxide), polyvinylidene fluoride and their copolymer composition.
In copolymer, the ratio of different repeat units can be controlled as scope commonly used in the art aptly, such as, control be
The scope of 0.01:0.99 to 0.99:0.01.
For implementing the mode of the present invention
Hereinafter, the method manufacturing graphene-based laminates 100 according to embodiments of the present invention will be described.
In the method manufacturing graphene-based laminates 100 according to embodiments of the present invention, first, the first substrate makes
Graphene growth is to form graphene layer 120.The first substrate as the Seed Layer for graphene growth can be not limited to specific
Material.Such as, the first substrate can include from by silicon (Si), nickel (Ni), cobalt (Co), ferrum (Fe), platinum (Pt), gold (Au), aluminum
(Al), chromium (Cr), copper (Cu), magnesium (Mg), manganese (Mn), molybdenum (Mo), rhodium (Rh), tantalum (Ta), titanium (Ti), tungsten (W), uranium (U), vanadium
(V), at least one metal or alloy selected in the group that zirconium (Zr), pyrite, bronze, copper-nickel alloy, rustless steel and germanium (Ge) form.
First substrate can include that catalyst layer is to promote the growth of Graphene.Catalyst layer can be not limited to specific material
Material.Such as, catalyst layer can be formed by the material identical or different with the material of the first substrate.The thickness of catalyst layer can not
Particularly limited.Catalyst layer can be thin layer or thick-layer.
Graphene can be made to grow in the first substrate by conventional chemical vapor deposition (CVD).The example of CVD has soon
Speed thermal chemical vapor deposition (RTCVD), inductively coupled plasma chemical gaseous phase deposition (ICP-CVD), low pressure chemical phase sink
Long-pending (LPCVD), sub-atmospheric CVD (APCVD), metal organic chemical vapor deposition (MOCVD) and plasma enhancing
Chemical gaseous phase deposition (PECVD).
Such as, in order to form graphene layer 120 in the first substrate, after the first substrate is installed in stove, can be greatly
Under air pressure, at a temperature of about 300 DEG C to about 2000 DEG C, the first substrate is carried out heat treatment, and supplies the reaction gas including carbon source
Body, so that graphene growth.
The example of carbon source has carbon monoxide, carbon dioxide, methane, ethane, ethylene, ethanol, acetylene, propane, butane, fourth two
Alkene, pentane, amylene, cyclopentadiene, hexane, hexamethylene, benzene and toluene.
Then, the graphene layer 120 of growth in the first substrate can be transferred to substrate 110, or be transferred on it arrange
There is the substrate 110 of the polymeric layer 130 of doping.
In this, can be by any rubbing method in various conventional rubbing methods (such as, spin coating, dip-coating or spraying)
The polymeric layer 130 making doping is formed in substrate 110.Such as, gathering in the doping by including ionic liquid and polymer
Compound is dissolved in suitable organic solvent after preparing coating solution, by spin coating, this coating solution can be applied to substrate
On 110, then it is dried to form the polymeric layer 130 of doping.
The transfer of graphene layer 120 can be performed by direct or indirect transfer method.Such as, can be by utilizing known volume
To volume technique, graphene layer 120 is transferred to substrate 110.Hereinafter, for the ease of describing, will be to by utilizing reel-to-reel
The method that graphene layer 120 transfers to substrate 110 is illustrated by technique.
Such as, substrate 110 can be made together with first substrate on it with graphene layer 120 through the roller list for stacking
Unit, this roller unit includes being arranged to multiple rollers relative to each other, be then passed through another roller unit (such as, including transferring roller) with
Graphene layer 120 is transferred to substrate 110, removes the first substrate by etching simultaneously.Available it is selectively etched out the
The etching solution of one substrate performs etching.Etching solution can be selected aptly according to the kind of the first substrate.
That is, superposed so that while the first suprabasil graphene layer 120 contacts substrate 110, making substrate 110
With on it with the first substrate of graphene layer 120 through transferring roller, so that the first suprabasil graphene layer 120 is transferred to base
The end 110, make substrate 110 and its upper the first substrate process with graphene layer 120 for being selectively etched out first simultaneously
The etching solution of substrate, thus graphene layer 120 is transferred in substrate 110 and by utilizing this etching solution to remove first
Substrate.
The polymeric layer 130 of doping can be formed between substrate 110 and graphene layer 120.In certain embodiments, can be
On transfer graphene layer 120 in substrate 110, form the polymeric layer 130 of doping.In some other embodiment, doping
Polymeric layer 130 be formed as two-layer, one layer in the most described two-layer between substrate 110 and graphene layer 120, and
And another layer is positioned on suprabasil graphene layer 120.Available known coating process forms the polymeric layer of doping
130。
As it has been described above, according to one or more embodiment of the present invention, can be by least one table at graphene layer
The polymeric layer of doping is formed to control the electric conductivity of graphene layer on face.The polymeric layer of doping can also protect graphene layer
And stablize graphene layer further.
Although described one or more of the present invention with reference to the accompanying drawings to show embodiment, but the common skill of this area
Art personnel, can at this it will be understood that in the case of without departing from the spirit and scope of the present invention being defined by the claims
To make the various changes in form and in details.
Industrial applicability
Graphene-based laminates according to any embodiment in above-described embodiment of the disclosure can include being arranged on graphite
The polymeric layer of the doping at least one surface of alkene layer, to control the electric conductivity of graphene layer.The polymeric layer of doping is also
Graphene layer can be protected and stablize graphene layer further.
Claims (8)
1. a graphene-based laminates, described graphene-based laminates includes:
Substrate；
Graphene layer, is arranged in substrate and includes at least one of which；And
Including the polymer sheet of the doping of organic adulterant, including gathering of the first doping being arranged between substrate and graphene layer
Compound sheet and the second polymer sheet adulterated being arranged on graphene layer, wherein, the polymer sheet and second of the first doping is mixed
Miscellaneous polymer sheet is separately positioned on the both sides of graphene layer,
Wherein, organic blended dose of the polymer sheet of doping is ionic liquid, and ionic liquid includes by chemical formula 1 and/or chemistry
The compound that formula 2 represents:
[chemical formula 1]
Wherein, in chemical formula 1, R1And R2Mutually the same or different from each other, and all independently be hydrogen, substituted or unsubstituted
C1～C16 alkyl, substituted or unsubstituted C2～C16 thiazolinyl, substituted or unsubstituted C2～C16 alkynyl, replacement or unsubstituted
C3～C16 cycloalkyl, substituted or unsubstituted C6～C16 aryl or substituted or unsubstituted C6～C20 heteroaryl；X-Table
Show the anion of ionic liquid,
[chemical formula 2]
Wherein, in chemical formula 2, R3And R4Mutually the same or different from each other, and all independently be hydrogen, substituted or unsubstituted
C1～C16 alkyl, substituted or unsubstituted C2～C16 thiazolinyl, substituted or unsubstituted C2～C16 alkynyl, replacement or unsubstituted
C3～C16 cycloalkyl, substituted or unsubstituted C6～C16 aryl or substituted or unsubstituted C6～C20 heteroaryl；X-Table
Show the anion of ionic liquid.
Graphene-based laminates the most according to claim 1, wherein, described substrate has the transparency, flexibility, ductility
Characteristic or the combination of these characteristics.
Graphene-based laminates the most according to claim 1 and 2, wherein, described substrate utilizes has the poly-of repetitive
Compound and manufacture, repetitive includes from by substituted or unsubstituted thiazolinyl, substituted or unsubstituted ester group, replacement or unsubstituted
Ether, substituted or unsubstituted carbonate group acrylate-based, substituted or unsubstituted, substituted or unsubstituted styrene
In the group of base, substituted or unsubstituted amide groups, substituted or unsubstituted imide and substituted or unsubstituted sulfuryl composition
At least one selected.
Graphene-based laminates the most according to claim 1 and 2, wherein, described substrate utilizes cellulose or includes fiber
Element polymer and manufacture.
Graphene-based laminates the most according to claim 1, wherein, the cation in chemical formula 1 includes from by 1,3-bis-
Methylimidazole., 1,3-diethyl imidazolium, 1-ethyl-3-methylimidazole, 1-butyl-3-Methylimidazole., 1-hexyl-3-
Methylimidazole., 1-octyl group-3-Methylimidazole., 1-decyl-3-Methylimidazole., 1-dodecyl-3-Methylimidazole. and
At least one selected in the group of 1-myristyl-3-Methylimidazole. composition.
Graphene-based laminates the most according to claim 1, wherein, the cation in chemical formula 2 includes from by 1-methyl
Pyridine, 1-ethylpyridine, 1-butyl-pyridinium, 1-ethyl-3-picoline, 1-butyl-3-picoline, 1-are own
At least one selected in the group of base-3-picoline and 1-butyl-3,4-lutidines composition.
Graphene-based laminates the most according to claim 1, wherein, the anion of the ionic liquid of chemical formula 1 and/or 2
It is organic anion or inorganic anion, and includes from by Br-、Cl-、I-、BF4 -、PF6 -、ClO4 -、NO3 -、AlCl4 -、
Al2Cl7 -、AsF6 -、SbF6 -、CH3COO-、CF3COO-、CH3SO3 -、C2H5SO3 -、CH3SO4 -、C2H5SO4 -、CF3SO3 -、(CF3SO2)2N-、(CF3SO2)3C-、(CF3CF2SO2)2N-、C4F9SO3 -、C3F7COO-(CF3SO2)(CF3CO)N-The group of composition selects
At least one.
8. according to the graphene-based laminates described in any one in claim 1,5 to 7, wherein, the polymer sheet of doping
Also include can be compatible with described ionic liquid polymer, can include from by polyethylene by the polymer compatible with described ionic liquid
Alcohol, polymethyl methacrylate, poly(ethylene oxide), poly(propylene oxide), polyvinylidene fluoride and the group of their copolymer composition
At least one of middle selection.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| KR10-2011-0087057 | 2011-08-30 | ||
| KR1020110087057A KR101275636B1 (en) | 2011-08-30 | 2011-08-30 | Laminate with graphene comprising doped-polymer layer |
| PCT/KR2012/006912 WO2013032233A2 (en) | 2011-08-30 | 2012-08-30 | Graphene-based laminate including doped polymer layer |
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| Publication Number | Publication Date |
|---|---|
| CN103890860A CN103890860A (en) | 2014-06-25 |
| CN103890860B true CN103890860B (en) | 2016-11-02 |
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Families Citing this family (16)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103345963B (en) * | 2013-06-28 | 2015-07-15 | 重庆墨希科技有限公司 | Graphene composite transparent electrode and preparation method and application thereof |
| CN104803371A (en) * | 2014-01-25 | 2015-07-29 | 福建省辉锐材料科技有限公司 | Graphene doping method |
| CN104803370A (en) * | 2014-01-25 | 2015-07-29 | 福建省辉锐材料科技有限公司 | Graphene transfer and doping method |
| CN105313394B (en) * | 2014-07-03 | 2018-08-03 | 陈汝霖 | A kind of human contact's property protective case containing two-dimentional hexagonal materials and preparation method thereof and application |
| CN104409177B (en) * | 2014-11-28 | 2017-02-22 | 中国科学院金属研究所 | Large-scale preparation method for stably-doped large-area graphene transparent conductive films |
| KR101911745B1 (en) * | 2015-03-23 | 2018-10-25 | 재단법인 나노기반소프트일렉트로닉스연구단 | Graphene laminate and method for preparing the same |
| EP3284718B1 (en) * | 2015-04-15 | 2020-06-10 | LG Electronics Inc. | Method for doping graphene, and graphene structure |
| KR102501463B1 (en) | 2015-05-21 | 2023-02-20 | 삼성전자주식회사 | Flexible device having flexible interconnect using 2 dimensional materials |
| KR101802601B1 (en) * | 2015-10-22 | 2017-11-30 | 한양대학교 산학협력단 | Functionalized graphene structures and method for manufacturing same |
| CN106115672B (en) * | 2016-06-23 | 2018-09-25 | 无锡格菲电子薄膜科技有限公司 | A kind of transfer method of graphene prepared by CVD method |
| CN106145098B (en) * | 2016-06-23 | 2019-01-11 | 无锡格菲电子薄膜科技有限公司 | A method of graphene is shifted by medium of glue film |
| CN106587038B (en) * | 2016-10-08 | 2019-05-24 | 无锡格菲电子薄膜科技有限公司 | A kind of preparation method of the treatment fluid of graphene film substrate, processing method and graphene film |
| US20180330842A1 (en) * | 2017-05-15 | 2018-11-15 | The Trustees Of Columbia University In The City Of New York | Layered metal-graphene-metal laminate structure |
| TWI691536B (en) * | 2017-10-25 | 2020-04-21 | 安炬科技股份有限公司 | Graphene polymer composite |
| KR102030265B1 (en) | 2018-02-26 | 2019-10-08 | 공주대학교 산학협력단 | Method for manufacturing nano composite of graphene with nacre structure |
| CN113382959A (en) * | 2018-11-30 | 2021-09-10 | 纽约州州立大学研究基金会 | Method for producing N-doped graphene films |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101462717A (en) * | 2007-12-17 | 2009-06-24 | 三星电子株式会社 | Single crystalline graphene sheet and process of preparing the same |
| CN101835609A (en) * | 2007-09-10 | 2010-09-15 | 三星电子株式会社 | Graphene sheet and process of preparing the same |
| CN102005301A (en) * | 2010-11-29 | 2011-04-06 | 华东师范大学 | Dye sensitized solar cell and preparation method thereof |
| CN102067323A (en) * | 2008-06-18 | 2011-05-18 | 巴斯夫欧洲公司 | Method for producing electrodes for solar cells |
| KR20110073222A (en) * | 2009-12-22 | 2011-06-29 | 광 석 서 | Graphene dispersions and graphene-ionic liquid polymer composites |
Family Cites Families (17)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US8785765B2 (en) * | 2003-07-14 | 2014-07-22 | Fujikura Ltd. | Electrolyte composition, photoelectric converter and dye-sensitized solar cell using same |
| WO2006049074A1 (en) * | 2004-11-01 | 2006-05-11 | Kaneka Corporation | Conductive composition, conductive molded body, conductive gel composition and method for producing same |
| KR100715548B1 (en) * | 2005-07-29 | 2007-05-07 | 광 석 서 | Conducting Polymer Synthesized with Partially Substituted Polymers as a Dopant |
| WO2008016990A2 (en) * | 2006-08-02 | 2008-02-07 | Ada Technologies, Inc. | High performance ultracapacitors with carbon nanomaterials and ionic liquids |
| EP2913881A1 (en) * | 2007-08-21 | 2015-09-02 | A123 Systems LLC | Electrochemical cell |
| KR101384665B1 (en) * | 2007-09-13 | 2014-04-15 | 성균관대학교산학협력단 | Transparent electrode comprising graphene sheet, display and solar cell including the electrode |
| WO2009120872A2 (en) * | 2008-03-26 | 2009-10-01 | Ada Technologies, Inc. | High performance batteries with carbon nanomaterials and ionic liquids |
| KR20090105761A (en) * | 2008-04-03 | 2009-10-07 | 삼성전자주식회사 | Cnt transparent electrode and method of manufacturing the same |
| WO2009134707A2 (en) * | 2008-04-27 | 2009-11-05 | Board Of Regents, The University Of Texas System | Ultracapacitors and methods of making and using |
| CN102224596B (en) | 2008-06-09 | 2015-06-17 | 三星电子株式会社 | Improved cnt/topcoat processes for making a transplant conductor |
| KR101212672B1 (en) * | 2008-12-26 | 2012-12-14 | 제일모직주식회사 | Conductive polymer, polymer composition, film and organic photoelectric device comprising same |
| CN102342013B (en) * | 2009-05-26 | 2014-07-16 | 阿尔卑斯电气株式会社 | Macromolecule actuator device |
| KR20110040223A (en) * | 2009-10-13 | 2011-04-20 | 동우 화인켐 주식회사 | Transparent electrode, manufacturing method thereof and electron device including the same |
| JP4527194B1 (en) | 2009-12-11 | 2010-08-18 | エンパイア テクノロジー ディベロップメント エルエルシー | Graphene structure, method for producing graphene structure, and electronic device |
| KR101680761B1 (en) * | 2010-09-17 | 2016-11-30 | 삼성전자주식회사 | Graphene-polymer layered composite and process for preparing the same |
| US20120277360A1 (en) * | 2010-10-28 | 2012-11-01 | Vorbeck Materials Corp. | Graphene Compositions |
| KR101166528B1 (en) * | 2011-07-29 | 2012-07-19 | 주식회사 엘엠에스 | Graphene laminate comprising dopants and preparation method of the same |
-
2011
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-
2012
- 2012-08-30 CN CN201280042456.3A patent/CN103890860B/en active Active
- 2012-08-30 US US14/239,599 patent/US9576695B2/en active Active
- 2012-08-30 WO PCT/KR2012/006912 patent/WO2013032233A2/en active Application Filing
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101835609A (en) * | 2007-09-10 | 2010-09-15 | 三星电子株式会社 | Graphene sheet and process of preparing the same |
| CN101462717A (en) * | 2007-12-17 | 2009-06-24 | 三星电子株式会社 | Single crystalline graphene sheet and process of preparing the same |
| CN102067323A (en) * | 2008-06-18 | 2011-05-18 | 巴斯夫欧洲公司 | Method for producing electrodes for solar cells |
| KR20110073222A (en) * | 2009-12-22 | 2011-06-29 | 광 석 서 | Graphene dispersions and graphene-ionic liquid polymer composites |
| CN102005301A (en) * | 2010-11-29 | 2011-04-06 | 华东师范大学 | Dye sensitized solar cell and preparation method thereof |
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| US20140234627A1 (en) | 2014-08-21 |
| US9576695B2 (en) | 2017-02-21 |
| WO2013032233A3 (en) | 2013-05-02 |
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